Slurry coating technique, as one of the most popular deposition methods, is widely used to produce various material coatings. This method includes two processes: spraying, brushing or dipping of slurry, and sintering heat treatment of the coated specimen. Superalloys and stainless steels are the most common materials used as either coating materials or substrate materials because of their excellent corrosion, wear, high-temperature and mechanical properties. This research is aimed at investigating the influence of the sintering heat treatment in the slurry coating process developed at Kennametal Stellite Inc. on the microstructure, hardness and wear behavior of superalloys and stainless steels. Low-carbon Stellite 22, cobalt-based Tribaloy T-400C, martensitic AISI 420 and AISI 440C stainless steels are studied in this research. The microstructure, hardness and wear resistance of these alloys before and after the heat treatment are investigated, stressing the influence of the heat treatment on these material characteristics. The hardness and wear tested are conducted on these alloys at both room temperature and at elevated temperatures. The worn surfaces of each specimen are analyzed using a Scanning Electron Microscope (SEM) with backscatter electron imaging (BEI) and energy dispersive X ray (EDX) spectrum. It is demonstrated that the heat treatment alters the microstructures of these alloys differently; it increases the hardness but affects the wear resistance more complexly than hardness. At room temperature, the wear resistance of these alloys is governed by their microstructures. However, at high temperatures, oxidation, resulting in formation of oxide films on the specimen surface, influences the wear resistance significantly.

Stainless steels were first developed in the early 20th century and have since then emerged as a very diverse class of engineering materials. Along with steels having new combinations of properties, there is a continuous development of new technologies allowing the material to be produced in a faster and more energy effcient manner. A prerequisite for new technologies to be adapted quicklyis a fundamental understanding of the microstructure evolution throughout theprocess chain. The first part of this thesis has been dedicated to the annealing and pickling processes from a process-microstructure perspective. In the second part the concept of utilising crystallographic texture as a way to attain microstructures with new combinations of properties has been evaluated. In the first part, annealing can be regarded as a high temperature oxidation process, resulting in chromium depletion that necessitate subsequent chemical pickling. Chemical pickling, on the other hand, is basically a wet-corrosion process and hence more difficult for highly corrosion-resistant grades. The chromium depleted layer was found to be enriched in austenite in case of duplex stainless steel UNS S32205 (Paper I) and this may inuence the pickling process. Proper pretreatment like shot-blasting dramatically increases the pickling rate because it provides the pickling acid with access to the chromium depleted layer (Paper II). Oxidation kinetics for S30400 in conditions relevant to strip annealing do not seem to be affected by the choice of air/oxygen as oxidiser even though the latter results in substantially higher water content (Paper III). This gives new possibilities regarding both cost savings and increased throughput. In the second part, the effect of crystallographic texture on resistance towards corrosion of S31603 in a solution of FeCl3 and AlCl3 in ethanol/glycerol and in 30 vol% H2SO4 is investigated. In the former, high density surfaces {1111} and {100} are less prone for pit nucleation, however the effect is relativelysmall. In H2SO4 pronounced crystallographic anisotropy is observed inwhich the corrosion rate increase in the order {111} &lt; {110} ≤ {100} (Paper IV).For corrosion at high temperatures, chromium diffusion is governed by randomhigh angle boundaries with ~20—55° misorientation. The possibilities to alter the texture in austenitic stainless steels by means of warm-rolling and annealing has been evaluated for S30403 and S31603. During warm-rolling, both steels develop the copper-type texture in contrast to the brass-type texture observedat room temperature. However only S30403 is prone to recrytallise cube texture during subsequent annealing (Paper V). / <p>QC 20150121</p>

A novel computer model of the evolution of columnar and equiaxed microstructure during alloy solidification has been developed. A control volume finite difference model of conduction heat transfer is applied to a two-dimensional domain bounded by a relatively cold mould. The initial condition is that of superheated liquid, and nucleation occurs either at the mould wall, leading to columnar dendritic growth, or within the bulk liquid, leading to the growth of equiaxed dendrites. The columnar front or the equiaxed grain boundaries are represented by computationally sharp interfaces, which separate liquid from partially solid alloy. Interpolation between discrete computational markers is employed to describe these interfaces, and a front-tracking technique is used to predict the evolution of the grain structure, via movement of the markers, across the fixed grid. The front velocity is determined via considerations of the kinetics of dendrite growth. The heat equation is fully coupled to the front-tracking algorithm by means of source terms which represent the evolution of latent heat due to the dendritic growth (advancing tips and thickening mushy zone). The model, applied to binary Al-Cu alloys, is computationally efficient. It predicts the variation of the extent of liquid undercooling ahead of the growing columnar front, and new metrics have been established to determine the likelihood of the formation of an equiaxed zone here. The employment of these metrics to establish the influence of heat extraction rate and alloy composition agrees with reports from the literature. The model does not distinguish between individual grains of the columnar zone, but it is shown that this is not an important limitation for most metal casting applications. Direct simulation of the nucleation and growth of multiple equiaxed crystals has been carried out, in which the nucleation and growth of individual grams can be observed via animation, and the influence of melt superheat and heat extraction rate on equiaxed solidification has been determined.

Radiation-induced changes in microstructures often lead to significant changes in mechanical properties of alloys used in the construction of nuclear reactors. It is desirable to test small specimens to make efficient use of the small volumes available in test and commercial reactor cores and also because small specimens are less affected by the sometimes steep flux gradients experienced in reactor cores and the sometimes large temperature gradients developed in the specimens from gamma heating. (Continues...).

The microstructure of low alloy Transformation Induced Plasticity (TRIP) assisted steels has been systematically varied through the combination of computational and experimental methodologies in order to enhance the mechanical performance and to fulfill the requirement of the next generation Advanced High Strength Steels (AHSS). The roles of microstructural parameters, such as phase constitutions, phase stability, and volume fractions on the strength-ductility combination have been revealed. Two model alloy compositions (i.e. Fe-1.5Mn-1.5Si-0.3C, and Fe-3Mn-1Si-0.3C in wt%, nominal composition) were studied. Multiphase microstructures including ferrite, bainite, retained austenite and martensite were obtained through conventional two step heat treatment (i.e. intercritical annealing-IA, and bainitic isothermal transformation-BIT). The effect of phase constitution on the mechanical properties was first characterized experimentally via systematically varying the volume fractions of these phases through computational thermodynamics. It was found that martensite was the main phase to deteriorate ductility, meanwhile the C/VA ratio (i.e. carbon content over the volume fraction of austenite) could be another indicator for the ductility of the multiphase microstructure. Following the microstructural characterization of the multiphase alloys, two microstructural design criteria (i.e. maximizing ferrite and austenite, suppressing athermal martensite) were proposed in order to optimize the corresponding mechanical performance. The volume fraction of ferrite was maximized during the IA with the help of computational thermodyanmics. On the other hand, it turned out theoretically that the martensite suppression could not be avoided on the low Mn contained alloy (i.e. Fe-1.5Mn-1.5Si-0.3C). Nevertheless, the achieved combination of strength (~1300MPa true strength) and ductility (~23% uniform elongation) on the low Mn alloy following the proposed design criteria fulfilled the requirement of the next generation AHSS. To further optimize the microstructure such that the designed criteria can be fully satisfied, further efforts have been made on two aspects: heat treatment and alloy addition. A multi-step BIT treatment was designed and successfully reduced the martensite content on the Fe-1.5Mn-1.5Si-0.3C alloy. Microstructure analysis showed a significant reduction on the volume fraction of martensite after the multi-step BIT as compared to the single BIT step. It was also found that, a slow cooling rate between the two BIT treatments resulted in a better combination of strength and ductility than rapid cooling or conventional one step BIT. Moreover, the athermal martensite formation can be fully suppressed by increasing the Mn content (Fe-3Mn-1Si-0.3C) and through carefully designed heat treatments. The athermal martensite-free alloy provided consistently better ductility than the martensite containing alloy. Finally, a microstructure based semi-empirical constitutive model has been developed to predict the monotonic tensile behavior of the multiphase TRIP assisted steels. The stress rule of mixture and isowork assumption for individual phases was presumed. Mecking-Kocks model was utilized to simulate the flow behavior of ferrite, bainitic ferrite and untransformed retained austenite. The kinetics of strain induced martensitic transformation was modeled following the Olson-Cohen method. The developed model has results in good agreements with the experimental results for both TRIP steels studied with same model parameters.

Low carbon bainitic steels microalloyed with Nb, Ti and V are widely used for the pipeline, construction and automobile industries because of their excellent combination of strength, toughness and weldability. Boron as another major alloying element has been also frequently used in this type of steels since the 1970s. The purpose of adding boron is to improve the hardenability of the steel by promoting bainite formation. / It has been realized that Boron can only be effective as a strengthening element when it is prevented from forming BN and/or Fe23(C, B) 6 precipitates. Therefore, Boron is always added together with other alloying elements which are stronger Nitride or Carbide formers, such as Ti and Nb. However, the formation of complex bainitic structures and the interaction with precipitates at industrial coiling temperature are not adequately understood. / In this study, the effect of boron on the microstructure and mechanical properties of a low carbon Nb-B steel was studied by a hot compression test (50% reduction at 850&deg;C) followed by quenching samples into a salt bath. The microstructures of the tested samples were examined through optical microscopy and SEM; and the mechanical properties of these samples were investigated by micro-hardness and shear punch tests. / The results indicate that during thermo-mechanical controlled rolling (TCR), the final properties of the products not only depend on the applied deformation but also depend on the coiling temperature where phase transformation takes place. According to the investigation, two strengthening mechanisms are responsible for the strength of the steel at the coiling temperature: phase transformation and precipitation. Under optical microscopy, the microstructures of all specimens appear to be bainite in a temperature range from 350&deg;C to 600&deg;C without distinct differences. However, the SEM micrographs revealed that the microstructures at 550&deg;C are very different from the microstructures transformed at the other holding temperatures. / Two strength peaks were observed at 350&deg;C and 550&deg;C in the temperature range studied. It is believed that the NbC precipitates are the main contributor to the peak strength observed at 550&deg;C because the kinetics of NbC is quite rapid at this temperature. The strength peak at 350&deg;C is mainly due to the harder bainitic phase, which formed at relatively lower temperature.

The high speed deformation behavior of a commercially available dual phase (DP) steel was studied by means of split Hopkinson bar apparatus in shear punch (25m/s) and tension (1000s-1) modes with an emphasis on the influence of microstructure. The cold rolled sheet material was subjected to a variety of heat treatment conditions to produce several different microstructures, namely ferrite plus pearlite, ferrite plus bainite and/or acicular ferrite, ferrite plus bainite and martensite, and ferrite plus different fractions of martensite. Static properties (0.01mm/s for shear punch and 0.001s -1 for tension) of all the microstructures were also measured by an MTS hydraulic machine and compared to the dynamic properties. The effects of low temperature tempering and bake hardening were investigated for some ferrite plus martensite microstructures. In addition, two other materials, composition designed as high strength low alloy (HSLA) steel and transformation induced plasticity (TRIP) steel, were heat treated and tested to study the effect of alloy chemistry on the microstructure and property relationship. / A strong effect of microstructure on both static and dynamic properties and on the relationship between static and dynamic properties was observed. According to the variation of dynamic factor with static strength, three groups of microstructures with three distinct behaviors were identified, i.e. classic dual phase (ferrite plus less than 50% martensite), martensite-matrix dual phase (ferrite plus more than 50% martensite), and non-dual phase (ferrite plus non-martensite). Under the same static strength level, the dual phase microstructure was found to absorb more dynamic energy than other microstructures. It was also observed that the general dependence of microstructure on static and dynamic property relationship was not strongly influenced by chemical composition, except the ferrite plus martensite microstructures generated by the TRIP chemistry, which exhibited much better dynamic factor values. This may suggest that solid solution strengthening should be more utilized in the design of crashworthy dual phase steels.

The research in this thesis aims to develop new mechanistic knowledge for coating processes at 2024-Al alloy surfaces, ultimately to aid the design of new protective coatings. Coatings formed by phosphating, chromating, and permanganating were characterized especially by scanning Auger microscopy (SAM), X-ray photoelectron spectroscopy, and scanning electron microscopy . The objective was to learn about growth (nm level) as a function of time for different coating baths, as well as a function of lateral position across the different surface microstructural regions, specifically on the μm-sized Al-Cu-Mg and Al-Cu-Fe-Mn particles which are embedded in the alloy matrix . The research characterizes coating thickness, composition, and morphology. The thesis emphasizes learning about the effect of different additives in zinc phosphating baths . It was found that the Ni²⁺ additive has two main roles : first, the rate of increase in local solution pH is limited by the slower kinetics of reactions involving Ni²⁺ compared to Zn²⁺, leading to thinner zinc phosphate (ZPO) coatings when Ni²⁺ is present. Second, most Ni²⁺ deposition occurs during the later stages of the coating process in the form of nickel phosphate and a Ni-Al oxide in the coating pores on the alloy surface, increasing the corrosion resistance. Aluminum fluoride precipitates first during the initial stages of the coating process, followed by aluminum phosphate, zinc oxide, and finally ZPO. When Ni²⁺ is present in the coating solution at 2000 ppm, ZnO predominates in the coating above the A-Cu-Fe-Mn particle while ZPO dominates on the rest of the surface. The Mn²⁺ additive gives a more even coating distribution (compared with Ni²⁺) across the whole surface. The Mn²⁺ -containing ZPO coating is similar to the chromate coating in terms of evenness, while there is more coating deposition at the second-phase particles for permanganate coatings. The oxides on the Al-Cu-Fe-Mn and matrix regions are similar before coating, thereby confirming that a variety of observed differences in ZPO coating characteristics at these regions arise from the different electrochemical characteristics of the underlying metals. Upon exposure to a corrosive solution, the ZPO coating provides more protection to the second-phase particles compared to the matrix.

Fundamental studies on the mechanisms and kinetics of reduction of dense synthetic nickel oxide have been carried out in H2-N2 and H2-H2O mixtures. The influences of temperature, hydrogen partial pressure, and hydrogen-steam ratio on the reduction process were systematically investigated. The kinetics of the reduction process were followed metallographically by measuring the advance of the nickel product layer. The microstructures of the reduction products and their changes during heating were characterized using a high resolution scanning electron microscopy. In H2-N2 mixtures and H2-H2O mixtures with low steam content, it was found that the initial reduction rates were first order with respect to hydrogen partial pressure. In both sets of mixtures, it was found that the progress of NiO reduction was not a monotonic function of temperature. A minimum rate of advancement of NiO reduction was observed in the temperature range 700oC – 800oC depending on the hydrogen partial pressures and reduction time. A number of distinctly different nickel product microstructures, originating at the Ni-NiO interface were observed under various reduction conditions, namely coarse fibrous nickel with fissures, fine porous nickel-planar interface, large porous nickel-irregular interface and dense nickel product layer. The microstructures of reduction product were found to change with temperature and time. It was found that heating the coarse fibrous nickel structure resulted in a re-crystallization, grain growth and densification of nickel product. When the heat treatments were carried out on the porous nickel structures, the number of pores decreases with increasing temperature and time, which was accompanied by the increase in the pore sizes. The microstructures and kinetics of the reduction of nickel oxide were found to be a function of temperature, gas composition and reaction time. The study provides strong evidence for a link between the reduction kinetics and the changes in the reduction product microstructures. Mechanisms and kinetics of the reduction of nickel oxide have been discussed by considering reduction conditions, information on the structures and elementary processes involving in the reduction process.

Thesis (Ph. D.)--University of Washington, 2007. / Vita. Includes bibliographical references (p. 133-150).